Oxidation colorants comprising 2-(2,5-diaminophenyl)-ethanol compounds and 2-chloro-6-methyl-3-aminophenol compounds

ABSTRACT

Oxidation dyes that contain a developer-coupler combination of 2-(2,5-diaminophenyl)-ethanol or its salt with an organic or inorganic acid and 2-chloro-6-methyl-3-aminophenol or its salt with an organic or inorganic acid are characterized by intensive blue finishes with high rubbing fastness.

BACKGROUND OF THE INVENTION

This invention relates to oxidation colorants containing a specialcombination of primary and secondary intermediates for coloring keratinfibers.

By virtue of their intensive colors and good fastness properties,so-called oxidation colorants play a prominent role in the coloring ofkeratin fibers, particularly human hair. Oxidation colorants containoxidation dye precursors, so-called primary intermediates and secondaryintermediates. The primary intermediates form the actual dyes with oneanother or by coupling with one or more secondary intermediates in thepresence of oxidizing agents or atmospheric oxygen.

Good oxidation dye precursors are expected to satisfy above all thefollowing requirements: they must form the required color tones withsufficient intensity and fastness during the oxidative couplingreaction. In addition, they must be readily absorbed onto the fiberswith no significant differences—particularly in the case of humanhair—between damaged and freshly regrown hair (levelling capacity). Theymust be resistant to light, heat and the effect of chemical reducingagents, for example permanent wave lotions. Finally, if they are used tocolor hair, they should not overly stain the scalp and, above all,should be toxicologically and dermatologically safe.

The primary intermediates normally used are primary aromatic aminescontaining another free or substituted hydroxy or amino group in thepara position or the ortho position, diaminopyridine derivatives,heterocyclic hydrazones, 4-aminopyrazolone derivatives and2,4,5,6-tetraaminopyrimidine and derivatives thereof.

Special representatives are, for example, p-toluylenediamine,2,4,5,6-tetraaminopyrimidine, p-aminophenol,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,2-(2,5-diaminophenyl)-ethanol, 2-(2,5-diaminophenoxy)-ethanol,1-phenyl-3-carboxyamido-4-amino-5-pyrazolone and 4-amino-3-methylphenol,2-hydroxy4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidineand 2,5,6-triaminohydroxypyrimidine.

The secondary intermediates used are generally m-phenylenediaminederivatives, naphthols, resorcinol and resorcinol derivatives,pyrazolones and m-aminophenols. Particularly suitable secondaryintermediates are α-naphthol, pyrogallol, 1,5-, 2,7- and1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol,resorcinol, resorcinol monomethyl ether, m-phenylenediamine,1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-amino-phenol,1,3-bis-(2,4-diaminophenoxy)-propane, 2-chlororesorcinol,2-chloro-6-methyl-3-aminophenol and 2-methyl resorcinol

By combination with various secondary intermediates, a certain primaryintermediate can form a broad range of color tones. Nevertheless, it isoften not possible to obtain the large range of natural color tones witha single primary intermediate. In practice, therefore, a combination ofvarious primary intermediates and secondary intermediates has to be usedto obtain a single natural-looking color. Accordingly, there is aconstant need for new improved secondary intermediate/primaryintermediate combinations. This applies in particular to the blues whereconventional dyes are often not entirely satisfactory in theirlevel-dyeing capacity and their resistance to cold waving and washing.

Accordingly, the problem addressed by the present invention was toprovide new primary intermediate/secondary intermediate combinations inthe blue range which would satisfy the requirements oxidation dyeprecursors are expected to meet to a particular degree.

It has now surprisingly been found that a special combination of a knownsecondary intermediate and a known primary intermediate leads to darkblue colors of high brilliance which are additionally distinguished byhigh fastness to rubbing.

DESCRIPTION OF THE INVENTION

The present invention relates to oxidation colorants for coloringkeratin fibers containing secondary intermediates and primaryintermediates in a water-containing carrier, characterized in that2-(2,5-diaminophenyl)-ethanol or a salt thereof with an inorganic ororganic acid is present as the primary intermediate while2-chloro-6-methyl-3-aminophenol or a salt thereof with an inorganic ororganic acid is present as the secondary intermediate.

In the context of the invention, keratin fibers are understood toinclude pelts, wool, feathers and, in particular, human hair. Althoughthe oxidation colorants according to the invention are particularlysuitable for coloring keratin fibers, there are no basic obstacles totheir use in other fields, particularly in color photography.

The primary intermediate according to the invention is already knownfrom DE-OS 28 31 847 to which reference is expressly made regarding theproduction of this compound.

The secondary intermediate according to the invention is known fromDE-OS 30 16 008 as a secondary intermediate for intensive blue tones inparticular. Accordingly, reference is expressly made to this documentalso.

However, there is no reference in either of these documents to thecombination according to the invention or even to its highlyadvantageous properties.

The primary and secondary intermediates according to the invention maybe used both as free bases and in the form of their inorganic or organicsalts, for example hydrochlorides or hydrobromides.

The hair colorants according to the invention contain both the primaryintermediates and the secondary intermediates in a quantity ofpreferably 0.01 to 20% by weight and, more preferably 0.5 to 5% byweight, based on the oxidation colorant as a whole. The primaryintermediates and secondary intermediates are generally used insubstantially equimolar quantities. Although the equimolar amounts ofprimary and secondary intermediates have proven expedient, a certainexcess of individual oxidation dye precursors is not a disadvantage, sothat the primary intermediates and secondary intermediates may bepresent in a molar ratio of 1:0.5 to 1:2.

In addition to the primary intermediate/secondary intermediatecombination according to the invention, the hair colorants mayoptionally contain other primary intermediates and/or secondaryintermediates to obtain special color tones. Suitable compounds werementioned in the acknowledgement of the prior art.

In one preferred embodiment, the hair colorants according to theinvention contain typical substantive dyes in addition to the oxidationdye precursors in quantities of 0.01 to 20% by weight, based on theoxidation hair colorant as a whole, for further modifying the colortones. The typical substantive dyes in question may be selected, forexample, from the group of nitrophenylenediamines, nitroaminophenols,anthraquinones or indophenols, for example the compounds known under theinternational names or trade names of HC Yellow 2, HC Yellow 4, BasicYellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue2, Nitroblau, Disperse Blue 3, Basic Blue 99, HC Violet 1, DisperseViolet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, picramicacid and Rodol 9 R.

The oxidation dye precursors and the substantive dyes optionally presentdo not have to be single compounds. Instead, the hair colorantsaccording to the invention—due to the processes used for producing theindividual dyes—may contain small quantities of other componentsproviding they do not adversely affect the coloring result or have to beruled out for other reasons, for example toxicological reasons.

To produce the colorants according to the invention, the oxidation dyeprecursors are incorporated in a suitable water-containing carrier. Forcoloring hair, such carriers are, for example, cremes, emulsions, gelsor even surfactant-containing foaming solutions, for example shampoos,foam aerosols or other formulations suitable for application to thehair.

The colorants according to the invention may also contain any of theknown active substances, additives and auxiliaries typical of suchformulations. In many cases, the colorants contain at least onesurfactant, both anionic and zwitterionic, ampholytic, nonionic andcationic surfactants being suitable in principle. In many cases,however, it has been found to be of advantage to select the surfactantsfrom anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants for the hair colorants according to theinvention are any anionic surface-active substances suitable for use onthe human body. Such substances are characterized by awater-solubilizing anionic group such as, for example, a carboxylate,sulfate, sulfonate or phosphate group and a lipophilic alkyl groupcontaining around 10 to 22 carbon atoms. In addition, glycol orpolyglycol ether groups, ester, ether and amide groups and also hydroxylgroups may also be present in the molecule. The following are examplesof suitable anionic surfactants—in the form of the sodium, potassium andammonium salts and the mono-, di- and trialkanol-ammonium saltscontaining 2 or 3 carbon atoms in the alkanol group:

linear fatty acids containing 10 to 22 carbon atoms (soaps),

ether carboxylic acids corresponding to the formulaR—O—(CH₂—CH₂O)_(x)—CH₂—COOH, in which R is a linear alkyl groupcontaining 10 to 22 carbon atoms and x=0 or 1 to 16,

acyl sarcosides containing 10 to 18 carbon atoms in the acyl group,

acyl taurides containing 10 to 18 carbon atoms in the acyl group,

acyl isethionates containing 10 to 18 carbon atoms in the acyl group,

sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbonatoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethylesters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6oxyethyl groups,

linear alkane sulfonates containing 12 to 18 carbon atoms,

linear α-olefin sulfonates containing 12 to 18 carbon atoms,

α-sulfofatty acid methyl esters of fatty acids containing 12 to 18carbon atoms,

alkyl sulfates and alkyl polyglycol ether sulfates corresponding to theformula R—O(CH₂—CH₂O)_(x)—OSO₃H, in which R is a preferably linear alkylgroup containing 10 to 18 carbon atoms and x=0 or 1 to 12,

mixtures of surface-active hydroxysulfonates according to DE-A-37 25030,

sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propyleneglycol ethers according to DE-A-37 23 354,

sulfonates of unsaturated fatty acids containing 12 to 24 carbon atomsand 1 to 6 double bonds according to DE-A-39 26 344,

esters of tartaric acid and citric acid with alcohols in the form ofaddition products of around 2 to 15 molecules of ethylene oxide and/orpropylene oxide with fatty alcohols containing 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ethersulfates and ether carboxylic acids containing 10 to 18 carbon atoms inthe alkyl group and up to 12 glycol ether groups in the molecule,sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbonatoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethylesters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6oxyethyl groups.

In the context of the invention, zwitterionic surfactants aresurface-active compounds which contain at least one quaternary ammoniumgroup and at least one —COO⁽⁻⁾ or —SO₃ ⁽⁻⁾ group in the molecule.Particularly suitable zwitterionic surfactants are the so-calledbetaines, such as N-alkyl-N,N-dimethyl ammonium glycinates, for examplecocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyl dimethyl ammoniumglycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolinescontaining 8 to 18 carbon atoms in the alkyl or acyl group andcocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theCTFA name of Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in additionto a C₈₋₁₈ alkyl or acyl group, contain at least one free amino groupand at least one —COOH or —SO₃H group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyl iminodipropionic acids,N-hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-cocoalkyl aminopropionate,cocoacyl aminoethyl aminopropionate and C₁₂₋₁₈ acyl sarcosine.

Nonionic surfactants contain, for example, a polyol group, apoly-alkylene glycol ether group or a combination of polyol andpolyglycol ether groups as the hydrophilic group. Examples of suchcompounds are

products of the addition of 2 to 30 moles of ethylene oxide and/or 0 to5 moles of propylene oxide to linear fatty alcohols containing 8 to 22carbon atoms, to fatty acids containing 12 to 22 carbon atoms and toalkylphenols containing 8 to 15 carbon atoms in the alkyl group,

C₁₂₋₂₂ fatty acid monoesters and diesters of products of the addition of1 to 30 moles of ethylene oxide to glycerol,

C₈₋₂₂ alkyl mono- and oligoglycosides and ethoxylated analogs thereof,

products of the addition of 5 to 60 moles of ethylene oxide to castoroil and hydrogenated castor oil,

products of the addition of ethylene oxide to sorbitan fatty acidesters,

products of the addition of ethylene oxide to fatty acid alkanolamides.

Examples of cationic surfactants suitable for use in the hair treatmentformulations according to the invention are, in particular, quaternaryammonium compounds. Preferred quaternary ammonium compounds are ammoniumhalides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethylammonium chlorides and trialkyl methyl ammonium chlorides, for examplecetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride,distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride,lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammoniumchloride. Other cationic surfactants suitable for use in accordance withthe invention are the quaternized protein hydrolyzates.

Also suitable for use in accordance with the invention are cationicsilicone oils such as, for example, the commercially available productsQ2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning 929 Emulsion (containing ahydroxylamino-modified silicone which is also known as Amodimethicone),SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer:Wacker) and Abil® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt;diquaternary polydimethyl siloxanes, Quaternium-80).

Alkyl amidoamines, particularly fatty acid amidoamines, such as thestearyl amidopropyl dimethyl amine obtainable as Tego Amid®S 18, aredistinguished not only by their favorable conditioning effect, but alsoand in particular by their ready biodegradability.

Quaternary ester compounds, so-called “esterquats”, such as the dialkylammonium methosulfates and methyl hydroxyalkyl dialkoyloxyalkyl ammoniummethosulfates marketed under the trade name of Stepantex®, are alsoreadily biodegradable.

One example of a quaternary sugar derivative suitable for use as acationic surfactant is the commercially available product Glucquat®100(CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride).

The compounds containing alkyl groups used as surfactants may be singlecompounds. In general, however, these compounds are produced from nativevegetable or animal raw materials so that mixtures with different alkylchain lengths dependent upon the particular raw material are obtained.

The surfactants representing addition products of ethylene and/orpropylene oxide with fatty alcohols or derivatives of these additionproducts may be both products with a “normal” homolog distribution andproducts with a narrow homolog distribution. Products with a “normal”homolog distribution are mixtures of homologs which are obtained in thereaction of fatty alcohol and alkylene oxide using alkali metals, alkalimetal hydroxides or alkyl metal alcoholates as catalysts. By contrast,narrow homolog distributions are obtained when, for example,hydrotalcites, alkaline earth metal salts of ether carboxylic acids,alkaline earth metal oxides, hydroxides or alcoholates are used ascatalysts. The use of products with a narrow homolog distribution can beof advantage.

Other active substances, auxiliaries and additives are, for example,

nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylatecopolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetatecopolymers and polysiloxanes,

cationic polymers, such as quaternized cellulose ethers, polysiloxanescontaining quaternary groups, dimethyl diallyl ammonium chloridepolymers, acrylamide/dimethyl diallyl ammonium chloride copolymers,dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymersquaternized with diethyl sulfate, vinyl pyrrolidone/imidazoliniummethochloride copolymers and quaternized polyvinyl alcohol,

zwitterionic and amphoteric polymers such as, for example,acrylamido-propyl/trimethyl ammonium chloride/acrylate copolymers andoctyl acrylamide/methyl methacrylate/tert.butyl aminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,

anionic polymers such as, for example, polyacrylic acids, crosslinkedpolyacrylic acids, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/ vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinyl ether/maleicanhydride copolymers and acrylic acid/ethyl acrylate/N-tert.butylacrylamide terpolymers,

thickeners, such as agar agar, guar gum, alginates, xanthan gum, gumarabic, karaya gum, carob bean flour, linseed gums, dextrans, cellulosederivatives, for example methyl cellulose, hydroxyalkyl cellulose andcarboxymethyl cellulose, starch fractions and derivatives, such asamylose, amylopectin and dextrins, clays such as, for example, bentoniteor fully synthetic hydrocolloids such as, for example, polyvinylalcohol,

structurants, such as glucose and maleic acid,

hair-conditioning compounds, such as phospholipids, for example soyalecithin, egg lecithin and kephalins, and also silicone oils,

protein hydrolyzates, more particularly elastin, collagen, keratin, milkprotein, soya protein and wheat protein hydrolyzates, condensationproducts thereof with fatty acids and quaternized protein hydrolyzates,

perfume oils, dimethyl isosorbide and cyclodextrins,

solubilizers, such as ethanol, isopropanol, ethylene glycol, propyleneglycol, glycerol and diethylene glycol,

dyes for coloring the formulations,

anti-dandruff agents, such as Piroctone Olamine and Zinc Omadine,

other substances for adjusting the pH value,

active substances, such as panthenol, pantothenic acid, allantoin,pyrrolidone carboxylic acids and salts thereof, plant extracts andvitamins,

cholesterol,

UV absorbers,

consistency promoters, such as sugar esters, polyol esters or polyolalkyl ethers,

fats and waxes, such as spermaceti, beeswax, montan wax, paraffins,fatty alcohols and fatty acid esters,

fatty acid alkanolamides,

complexing agents, such as EDTA, NTA and phosphonic acids,

swelling and penetration agents, such as glycerol, propylene glycolmonoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas andprimary, secondary and tertiary phosphates,

opacifiers, such as latex,

pearlescers, such as ethylene glycol mono- and distearate,

propellents, such as propane/butane mixtures, N₂O, dimethyl ether, CO₂and air and

antioxidants.

To produce the colorants according to the invention, the constituents ofthe water-containing carrier are used in the usual quantities for thispurpose. For example, emulsifiers are used in concentrations of 0.5 to30% by weight while thickeners are used in concentrations of 0.1 to 25%by weight, based on the colorant as a whole.

Basically, the color may be oxidatively developed with atmosphericoxygen. However, a chemical oxidizing agent is preferably used,particularly when human hair is to be not only colored, but alsolightened. Particularly suitable oxidizing agents are hydrogen peroxideor addition products thereof with urea, melamine or sodium borate.Oxidation may also be carried out with enzymes. In this case, theenzymes may be used both to produce oxidizing per compounds and toenhance the effect of an oxidizing agent present in small quantities.One example of an enzymatic process is the procedure whereby the effectof small quantities (for example 1% and less, based on the formulationas a whole) of hydrogen peroxide is enhanced by peroxidases.

The preparation of the oxidizing agent is best mixed with thepreparation of the oxidation dye precursors immediately before coloringof the hair. The ready-to-use hair coloring preparation formed shouldpreferably have a pH value of 6 to 10. In a particularly preferredembodiment, the hair colorant is used in a mildly alkaline medium. Theapplication temperatures may be in the range from 15 to 40° C. After acontact time of about 30 minutes, the hair colorant is removed from thehair to be colored by rinsing. There is no need for the hair to bewashed with a shampoo where a carrier of high surfactant content, forexample a coloring shampoo, has been used.

The following Example is intended to illustrate the invention.

EXAMPLE

A cream base of the following composition was initially prepared:

Tallow fatty alcohol 17.0 Lorol ® techn.¹ 4.0 Texapon ® N 28² 40.0Dehyton ® K³ 25.0 Eumulgin ® B 2⁴ 1.5 Distilled water 12.5

¹ C₁₂₋₁₈ fatty alcohol (HENKEL)

² Sodium lauryl ether sulfate (ca. 28% active substance; CTFA name:Sodium Laureth Sulfate) (HENKEL)

³ Fatty acid amide derivative of betaine structure with the formulaR—CONH(CH₂)₃N⁺(CH₃)₂CH₂COO⁻(ca. 30% active substance; CTFA nameCocoamidopropyl Betaine) (HENKEL)

⁴ Cetostearyl alcohol containing around 20 moles of EO (CTFA name:Ceteareth-20) (HENKEL)

On the basis of this cream, the following hair coloring cream emulsionwas then prepared:

Cream base 50.0 Primary intermediate 7.5 mmoles Secondary intermediate7.5 mmoles Na₂SO₃ (inhibitor) 1.0 (NH₄)₂SO₄ 1.0 Conc. ammonia solutionto pH 10 Water to 100

The components were mixed with one another in the above order. Afteraddition of the oxidation dye precursors and the inhibitor, the pH valueof the emulsion was initially adjusted to 10 with concentrated ammoniasolution, after which the emulsion was made up with water to 100 g.

The color was oxidatively developed with 3% hydrogen peroxide solutionas oxidation solution. To this end, 50 g of hydrogen peroxide solution(3%) were added to and mixed with 100 g of the emulsion.

The coloring cream was applied to approximately 5 cm long tresses ofstandardized, 90% grey, but not specially pretreated human hair and leftthereon for 30 minutes at 32° C. After the coloring process, the hairwas rinsed, washed with a standard shampoo and then dried.

The color obtained with the primary intermediate/secondary intermediatecombination according to the invention was dark blue. The fastness ofthe colored hair to rubbing was very high.

In addition, the colors obtained with the following hair coloring creamemulsions based on the above-mentioned formulation were investigated:

B1 B2 B3 Primary intermediate: 2-(2,5-Diaminophenyl)- 7.5 mmoles 7.5mmoles 7.5 mmoles ethanol Secondary intermediate: 2-Chloro-6-methyl-3-7.5 mmoles 7.5 mmoles 7.5 mmoles aminophenol Other components:5-Amino-2-methyl phenol 0.025 — 0.05 4-(N-2-Hydroxyethyl)-3-nitro- 0.25— — aniline 2-Amino-6-chloro-4-nitro- — 0.25 — phenol Resorcinol — 0.17— 2,4,5,6-Tetraaminopyrimidine — — 0.13 Color Magenta Intensive Violetbrown

What is claimed is:
 1. An oxidation colorant for coloring keratinfibers, comprising a primary intermediate selected from the groupconsisting of 2-(2,5-diaminophenyl)-ethanol and organic or inorganicacid salts thereof, a secondary intermediate selected from the groupconsisting of 2-chloro-6-methyl-3-aminophenol and organic or inorganicacid salts thereof, and a water-containing carrier.
 2. An oxidationcolorant according to claim 1, wherein the primary intermediatecomprises 0.01% to 20% by weight and the secondary intermediatecomprises 0.01% to 20% by weight, said weight percents based on theweight of the oxidation colorant as a whole.
 3. An oxidation colorantaccording to claim 2, wherein the primary intermediate comprises 0.5% to5% by weight and the secondary intermediate comprises 0.5% to 5% byweight, said weight percents based on the weight of the oxidationcolorant as a whole.
 4. An oxidation colorant according to claim 3,further comprising at least one other primary intermediate or at leastone other secondary intermediate.
 5. An oxidation colorant as claimed inclaim 4, further comprising a substantive dye.
 6. An oxidation colorantas claimed in claim 5, further comprising a surfactant.
 7. An oxidationcolorant according to claim 3, wherein the primary intermediate is2-(2,5-diaminophenyl)-ethanol and the secondary intermediate is2-chloro-6-methyl-3-aminophenol.
 8. A method of coloring keratin fibers,comprising preparing an oxidation colorant according to claim 1,contacting said oxidation colorant with an oxidizing agent selected fromthe group consisting of atmospheric oxygen, peroxides, and peroxidases,and applying said oxidation colorant contacted with said oxidizing agentto a fiber to effect coloration thereof.
 9. A method according to claim8, wherein the primary intermediate is 2-(2,5-diaminophenyl)-ethanol,the secondary intermediate is 2-chloro-6-methyl-3-aminophenol, and theoxidizing agent is hydrogen peroxide or an addition product thereof withurea, melamine, or sodium borate.